Derivative of polymerized cyanoanthraquinone compounds



' naphthalene and the like.

Patented Jan. 17, 1933 UNITED STATES PATENT OFFICE MAX ALBERT K'UNZ, OF MANNI-IEIM, AND KARL KOEBERLE, OF LUDWIGSHAFEN-ON- THE-RHINE, GERMANY, ASSIGNQBSTO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE l r DERIVATIVE F POLYMERIZED GYANOANTHRAQUINONE COMPOUNDS No Drawing. Application filed November12, 1930, Serial No; 495,281, and in Germany Novemb er 18,1929.

The present invention relates to derivatives of polymerized cyanoanthraquinone compounds and process of producing the same.

Vile have found that new derivatives of polymerized cyanoanthraquinone compounds which are valuable partly as dyestufi'sand partly as intermediate productsare obta ned 10 by treatingamino derivatives of polymerized cyanoanthraquinone compounds of the general formula:

NRCN; [Y/ :L in which w is the number of molecules which are joined together by the polymerizat on (probably 3) R is an anthraquinone radicle which may contain, besides the amino group indicated, further amino groups or other substituents and Y is hydrogen or an alkyl group, for example a methyl or an ethyl group, with acylating agents. As the polymerized cyanogen compounds are'to be understood substances of the kind which-are obtainable according to the British Patent Specifications Nos. 309,193 and 309,45lor by treatment of amino derivatives of cyanoan- V thraquinones with condensing agents, as'for example strong acids,'such as sulphuric acid, chlorosulphonic acid, phosphoric acid and hydrochloric acid, or alkaline condensing agents. I

The reaction may be carried out in the presence or absence of diluents, and of agents for combining with acids. Indifferent aromatic solvents of high boiling point may be employed for the purpose of our invention, for example, nitrobenzene, trichlorobenzene, As acylating agents the halides and anhydrides of organic acids may be used, such as for example the aromatic acids, such as benzoic acid, for inmaterial are quite fast to chlorine. halides and anhydrides of aliphatic acid, r such as acetic acid and propionic acid, or

stance benzoyl chloride, benzo-trichloride, or the said derivatives of naphthoic acid and phthalic acid. The reaction products are usually obtained in very good yields and in a crystalline form. If desired they may be purified by the usual methods, such as crystallization,sublimation, extraction by means of organic solvents, purification by way of their sulphates, or treatment with oxidizing agents, as for example with sodium hypochlorite.

, The followingexamples will further illustrate the nature of this invention, but the invention is not restricted to these examples. The parts are by weight.

Example 1 theform of fine yellow needles is filtered Off by suction, Washed with Water oral cohol if desired and dried. It is very difiicultly soluble in all'organic solvents, crystallizes from 4100 to 500-. parts of nitrobenzene in the form of yellow needles, dissolves in concentrated sulphuric acid giving an olive-yellow coloration anddyes the vegetable fibre from a brown alkaline hydrosulphite vat powerful clear greenish yellow shades of very good fastness, especially of excellent fastness to kier boiling and bucking and which, contrastedwith'the orange dyeings of the initial The reaction may also be carried out in the presence of nitrobenzene or another organic dlluent.

polymerized pounds, whlch comprises treating an ammo Dyestuffs giving lemon yellow and green yellow dyeings are obtained with para-chlorobenzoyl chloride and with metamethoxybenzoyl chloride respectively.

Reaction products which are obtained in an insufficiently pure form may be purified in the form of their aqueous pastes with sodium hypochlorite solution. I

The polymerization product of l-ainino-Q- cyanoanthraquinone may also be benzoylated in the beforedescribed manner.

EwampZ-e 2 initial material employed in Example 1 (obtained by treatment with bromine in chlorosulphonic acid) are suspended in 300 parts of benzoyl chloride and boiled while stirring until the suspension has become pure yellow in color. The whole is then allowed to cooland is worked up in the manner decribed in Example 1. The reaction product containing bromine obtained forms yellow needles, dissolves in concentrated sulphuric acid giving an olive coloration and dyes cotton from a brown vat yellow shades of very goodfastness.

A dyestufi' giving yellow dyeings is obtained in an analogous manner by the action of benzoyl chloride on polymerized l-bromo- 2 -amino 3 cyanoanthraquinon (obtainable by heating the 1bromo-2 amino.3ecyanoanthraquinone, obtained by brominating 2-amino-3-Icyanoanthraquinone in aqueous suspension, in quinoline with cuprous salts according to the British Patent Specification No. 309,193).

What we claim is 1. A process ofproducing derivatives of cyanoanthraquinone comderivative of a polymerized cyanoanthraquinone corresponding to the general formula in which 00 is probably 3, R stands for, an anthraquinone radicle, and Y for hydrogen or an alkyl group, with an acylating agent.

2. A process of producing derivatives of polymerized cyanoanthraquinone compounds which comprises treating an amino derivative of a polymerized cyano-anthraquinone corresponding to the general formula in which w is probably 3, R stands; for an anthraquinone radicle, and Y for hydrogen or an alkyl group, with an acylating agentin an indifferent aromatic diluent of high boiling point. A V

3. As new articles of manufacturederiva- 50 parts of the bromination product of the shades.

tives of polymerized cyanoanthraquinone corresponding to the formula N-R-ON Y a:

in which w is probably 3, R stands for an anthraquin-one radicle, Y for hydrogen or an alkyl group and Z for an acyl group, the said derivatives being 'difiicultly soluble in or- "7 ganio solvents, soluble in concentrated sulphuric acid to give olive colorations and dyeing cotton from brown vats yellow shades.

4. As a new article of manufacture the derivative of polymerized 2-amino-3-cyano 'antihraquinone corresponding Etc '1 the 5 formu a derivative of polymerized Q-aminQrEB- yanor anthraquinone corresponding to the for.-

o l I V ON 3 ll 0 z in which 00 is probably 8, the said derivative forming yellow needles dificultly soluble. in organic solvents, dissolving in concentrated sulphuric acid to give an olive coloration and dyeing cotton from a brown vat yellow 6. A process of producing derivatives of polymerized cyanoanthraquinone.compounds, which comprises treating an amino derivative of a polymerized cyanoanthraquinone corresponding to the general formula i in which m is probably 3, It stands for" an anthraquinone radicle which may be Substi- 1'20 tuted by amino or halogen and Y for hydrogen or an alkyl group, with an acylating agent. 7 I V 7. As new articles of manufacture derivatives of polymerized cyanoanthraquinone 125 corresponding to the formula:

in which a: isprobably 3, R fstandsfor an 'anthraquinone radicle which may be substituted by amino or halogen, Y for hydrogen or an alkyl group and Z for an acyl group, the said derivatives being diflicultly soluble in organic solvents, soluble in concentrated sulphuric acid to give olive colorations and dyeing cotton from brown vats yellow shades.- 8. A process of producing derivatives of polymerized cyanoanthraquinone compounds, 19 which comprises treating an amino derivative of a polymerized oyanoanthraquinone corresponding to the general formula:

in which :2 is probably 3, R stands for a grouping comprising a single anthraquinone nucleus to which the ON and groups are directly attached, and Y stands for hydrogen or an alkyl group, with an acylating agent. i

9. As new articles of manufacture derivatives of polymerized cyanoanthraquinone corresponding to the formula:

in which it is probably 3, B stands for a grouping comprising a single anthraquinone nucleus to which the ON and \Y groups are directly attached, Y stands for 40 hydrogen or an alkyl group and Z for an acyl group, the said derivatives being difiicultly soluble in organic solvents, soluble in concentrated sulphuric acid to give olive colorations and dyeing cotton yellow shades from brown vats. r

' In testimony whereof we have hereunto set our hands.

MAX ALBERT KUNZ. KARL KOEBERLE. 

